CN109082126B - Glucose response driven hydrogel multistage motor and preparation method thereof - Google Patents
Glucose response driven hydrogel multistage motor and preparation method thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 66
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 30
- 239000008103 glucose Substances 0.000 title claims abstract description 30
- 230000004044 response Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920001817 Agar Polymers 0.000 claims abstract description 80
- 239000008272 agar Substances 0.000 claims abstract description 80
- 108010010803 Gelatin Proteins 0.000 claims abstract description 77
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- 235000019322 gelatine Nutrition 0.000 claims abstract description 77
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 77
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 63
- 239000011259 mixed solution Substances 0.000 claims abstract description 49
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- 239000000741 silica gel Substances 0.000 claims abstract description 22
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 22
- 239000000499 gel Substances 0.000 claims description 70
- 229940094522 laponite Drugs 0.000 claims description 44
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims description 44
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- 238000000034 method Methods 0.000 claims description 22
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 7
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 claims description 5
- YNDRELOQYVNSSK-UHFFFAOYSA-N 2-methylprop-2-enamide;phenylboronic acid Chemical compound CC(=C)C(N)=O.OB(O)C1=CC=CC=C1 YNDRELOQYVNSSK-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- ULVXDHIJOKEBMW-UHFFFAOYSA-N [3-(prop-2-enoylamino)phenyl]boronic acid Chemical compound OB(O)C1=CC=CC(NC(=O)C=C)=C1 ULVXDHIJOKEBMW-UHFFFAOYSA-N 0.000 claims description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 5
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- 206010063385 Intellectualisation Diseases 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 7
- 239000002064 nanoplatelet Substances 0.000 description 7
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- 229910021642 ultra pure water Inorganic materials 0.000 description 6
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- 230000003197 catalytic effect Effects 0.000 description 3
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- -1 phenyl boronic acid compound Chemical class 0.000 description 3
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000011147 inorganic material Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
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Abstract
The invention discloses a glucose response driven hydrogel multistage motor and a preparation method thereof. The preparation of the hydrogel multistage motor is divided into two parts, a mold is made of silica gel, a movable small silica gel mold block is added in the middle of a mold hole when a driving layer is prepared, after the driving layer is prepared, the movable small silica gel mold block is taken out, gelatin/agar mixed solution with different proportions is dripped into an interval area, and finally the gelatin/agar mixed solution is gelatinized to form the hydrogel multistage motor which has glucose response, can be driven quickly and is intelligent. After the hydrogel multistage motor is formed, the motor is self-driven in a driving solution, the hydrogel multistage motor has excellent driving performance, the highest driving average speed can reach 16.2 +/-1.3 mm/s, a decomposition layer can be gradually dissolved through temperature control or infrared irradiation, and a small motor is gradually released and freely propelled. Compared with the traditional motor, the hydrogel multistage motor has the advantages of higher driving speed, more intellectualization and stronger controllability.
Description
Technical Field
The invention relates to the field of functional polymer materials, in particular to a glucose response driven hydrogel multistage motor and a preparation method thereof.
Background
In biological systems, many biomolecular machines are capable of autonomous driving in the presence of external fuel, inspired by biomolecular machines, researchers developed various artificial motors capable of autonomous driving in a liquid environment. In recent years, the development of the field of intelligent machines is receiving more and more attention, and motors made of metal and inorganic materials are still deficient in the aspect of intelligent application, and the controllability of the motors is weak. The hydrogel has the following excellent characteristics: good biocompatibility, strong hydrophilicity, softness and toughness, and capability of keeping a certain shape and making corresponding response to external environment stimulus, so that the development of the field of intellectualization is receiving more and more attention. Therefore, the hydrogel micro motor which is more intelligent and has stronger controllability is prepared by utilizing the excellent characteristics of the hydrogel, different structural designs and different external stimuli to realize the functionalized hydrogel and referring to the special functions of the large motor. Currently, the driving power source of hydrogel motorsMainly catalytic driving, marangoni effect and the like. The hydrogel secondary motor prepared by using Ag nano particles has very excellent driving performance (J.Mater.chem.A., 2017,5, 18442-18447), but the catalytic hydrogel secondary motor can only be used in H2O2Ambient driving, H2O2Can poison living cells, which limits the application of hydrogel motors in the biological field. Therefore, an environment-friendly energy source is searched for as a driving fuel of the hydrogel motor, and the hydrogel multistage motor which is more intelligent and has stronger controllability is prepared by adopting different structures.
Disclosure of Invention
The invention aims to provide a hydrogel multistage motor with alternating driving layers and decomposition layers, wherein the driving layer of the hydrogel multistage motor is phenylboronic acid hydrogel with glucose response driving, the decomposition layer is gelatin/agar mixed gel capable of realizing gel-sol conversion at low temperature, and the dissolution temperature of the gel is continuously increased along with the increase of the agar content, so that in the hydrogel multistage motor, the decomposition layers adopt the gelatin/agar mixed gel with different proportions, different dissolution temperatures of each decomposition layer in the multistage motor are realized, and good control is provided for the small motors for gradual dissolution and release of the decomposition layers. Interestingly, the hydrogel multistage motor has excellent driving performance in a glucose solution, and the driving speed can reach 16.2 +/-1.3 mm/s. The initial temperature of the driving solution is 28 ℃, the small motors which are dissolved and released step by step and can control the decomposition layers by adjusting the temperature are adopted, after the whole multi-stage motor is driven for a period of time, the temperature is raised, after the second-stage decomposition layer is dissolved, the first-stage small motor is released and freely propels, the motor at the front end can continue to move forward, and after the motor is transported to a specific position, the temperature is raised again, the fourth-stage decomposition layer is dissolved, and the third-stage small motor is released and freely propels. Meanwhile, a proper amount of graphene nanosheets are added into the gelatin/agar mixed gel, the decomposition layer is irradiated step by near infrared light (NIR), the decomposition layer absorbs NIR heat, the temperature rises, the decomposition layer is dissolved step by step, the small motor is released step by step and is driven freely, and the introduction of the NIR realizes more intelligent control over the step by step dissolution of the decomposition layer of the hydrogel multi-stage motor to release the small motor.
The invention also aims to provide a preparation method of the glucose response driven hydrogel multistage motor, which has the advantages of simple process, mild preparation conditions, low equipment requirements and good application prospect.
The purpose of the invention is realized by the following technical scheme.
A hydrogel multistage motor driven by glucose response is characterized in that a driving layer of the hydrogel multistage motor is phenyl boric acid hydrogel driven by glucose response, a decomposition layer is gelatin/agar mixed gel capable of realizing gel-sol conversion at low temperature, and the dissolution temperature of the gelatin/agar mixed gel is continuously increased along with the increase of agar content, so that in the hydrogel multistage motor, the decomposition layer adopts the gelatin/agar mixed gel with different proportions, different dissolution temperatures of each decomposition layer in the hydrogel multistage motor are realized, and good control is provided for gradually dissolving and releasing a small motor of the decomposition layer.
The preparation method of the hydrogel multistage motor driven by glucose response comprises the following steps of preparing a driving layer based on glucose response, preparing a decomposition layer with temperature or infrared control capable of being dissolved in a driving environment on the basis, manufacturing a mold by using silica gel, adding a movable small silica gel mold block in the middle of a mold hole when the driving layer is prepared, taking out the movable small silica gel mold block after the driving layer is prepared, dropwise adding gelatin/agar mixed solutions with different proportions into an interval area, and finally placing the mixed solutions in a refrigerator to gelatinize the solutions at low temperature, so that the hydrogel multistage motor with glucose response, quick driving and intelligence is formed, and the preparation method comprises the following steps:
(1) dispersing the dried laponite in water, stirring, and ultrasonically treating in an ice bath to form a uniform laponite dispersion liquid;
(2) adding a water gel monomer, a chemical cross-linking agent and a surfactant into the laponite dispersion liquid obtained in the step (1), stirring and dispersing uniformly, adding a photoinitiator and a catalyst under the condition of keeping out of the sun, ultrasonically mixing the mixed liquid uniformly in an ice bath, and introducing nitrogen to remove oxygen dissolved in the mixed liquid;
(3) adding movable small silica gel mold blocks into a large mold hole, injecting the mixed solution obtained in the step (2) into the large mold hole, polymerizing under a high-intensity ultraviolet lamp after all the mold holes are injected, and taking out the movable small silica gel mold blocks after the polymerization is finished to obtain a driving layer in the mold;
(4) preparing gelatin/agar mixed solutions with different ratios, wherein each decomposition layer adopts gelatin/agar mixed gel with different ratios, and the content of agar in the decomposition layer is gradually increased; in the temperature-controlled dissolving process, in order to better observe the dissolving phenomenon of a decomposition layer in a driving environment, a gelatin/agar mixed solution is dyed by using a water-soluble dye; meanwhile, in the infrared irradiation dissolving process, in order to enable the decomposition layer to obtain more energy from the infrared laser, adding graphene nanosheets into the gelatin/sol mixed solution;
(5) and (3) after the driving layer is obtained in the step (3), dripping the gelatin/agar mixed solution with different ratios obtained in the step (4) into a spacing area in a mould, standing to gelatinize the mixed solution, and separating from the mould to obtain the hydrogel multistage motor with the driving layer and the decomposition layer alternated.
Preferably, the laponite in the step (1) is used as a physical cross-linking agent of the hydrogel, and the laponite not only can enhance the mechanical property of the hydrogel, but also is beneficial to improving the dispersion of the phenyl boronic acid compound with certain hydrophobicity in the solution, and the amount of the laponite is 0.5-2% of the mass of the water in the step (1).
Preferably, the hydrogel monomer in step (2) is two types of monomers, namely an olefin water-soluble monomer with a double bond and an amide group and an olefin hydrophobic monomer with a phenylboronic acid group.
Further preferably, the olefin water-soluble monomer is one or more of acrylamide and N-isopropylacrylamide; the olefin hydrophobic monomer is one or more of 3-acrylamido phenylboronic acid and methacrylamide phenylboronic acid; the olefin hydrophobic monomer accounts for 25 to 40 percent of the mass of the olefin water-soluble monomer; the dosage of the olefin hydrophobic monomer is 1.5-2.5% of the mass of the water in the step (1).
Preferably, the chemical cross-linking agent in the step (2) is N, N-methylene bisacrylamide, and the using amount of the chemical cross-linking agent is 0.50-1.5% of the mass of the water in the step (1);
preferably, the surfactant in the step (2) is sodium dodecyl sulfate or polyethylene glycol, and the using amount of the surfactant is 1.5-2.0% of the mass of the water in the step (1);
preferably, the photoinitiator in the step (2) is 2,2' -azo (2-methylpropylamidine) dihydrochloride or alpha-aminoacetophenone, and the amount of the photoinitiator is 0.25 to 0.45 percent of the mass of the water in the step (1);
preferably, the catalyst in the step (2) is N, N, N ', N' -tetramethylethylenediamine or tetramethylethylenediamine, and the amount of the catalyst is 0.5-2.0% of the volume of the water in the step (1).
Preferably, the volume of the mixed solution injected into the single well of the mold in step (3) is 10. mu.l to 25. mu.l, and then the driving layer is obtained by photo-initiated polymerization.
Preferably, the total mass of the gelatin and the agar in the gelatin/agar mixed solution in the step (4) is 5 to 15% relative to the mass of the water in the step (1), wherein the mass of the agar relative to the gelatin is 0 to 20%.
Preferably, the graphene nanoplatelets of step (4) account for 1% to 4% of the gelatin/agar mixture mass.
Preferably, the volume of the gelatin/agar mixed solution injected into each well of the spaced molds in step (5) is the same as the volume of the actuating layer in step (3), and is 10. mu.l to 25. mu.l.
Preferably, the step (5) of gelling the solution is performed by placing the solution in a refrigerator at 4 ℃ for 2 to 5 hours.
Preparing a driving solution, in order to observe the driving process of the hydrogel multistage motor, adopting a glucose solution as a driving energy source, adjusting the pH value of the solution to be 8 by using sodium bicarbonate, adjusting the ionic strength of the driving solution by using sodium chloride, and setting the initial temperature of the environment to be 28 ℃; the concentration of glucose in the driving solution is 0.02-0.05 mol/L, the pH value of the adjusting solution is 8, and the ionic strength is 0.10-0.30 mol/L.
The second-stage decomposition layer is released and freely advanced by the first-stage small motor after being dissolved by temperature control or infrared irradiation, and the third-stage small motor is released and freely advanced after the fourth-stage decomposition layer is dissolved, and the whole process is realized in a driving solution.
Compared with the prior art, the invention has the following advantages and technical effects:
1) the hydrogel multistage motor with the driving layer and the decomposition layer alternated is prepared for the first time, the hydrogel multistage motor can be driven by itself in a glucose solution, the decomposition layer can be dissolved step by step through temperature control or infrared irradiation, and the small motor releases step by step and is propelled freely. Compared with the traditional motor, the hydrogel multistage motor has the advantages of higher driving speed, more intellectualization and stronger controllability.
2) The invention realizes the preparation of the hydrogel multistage motor with the driving layer and the decomposition layer alternated by utilizing the characteristic that the gelatin/agar mixed solution is easy to gel at low temperature.
3) The self-driving method utilizes the glucose responsiveness of the phenylboronic acid in the driving layer to realize the self-driving of the hydrogel multistage motor in the environment-friendly glucose solution. In the equilibrium state, the phenylboronic acid compound has two different forms: an uncharged hydrophobic form and a charged hydrophilic form. After glucose is added, a stable compound is formed by the charged hydrophilic form of the phenylboronate and the glucose, in order to balance two forms of the phenylboronic acid compound, the uncharged hydrophobic form is continuously converted into the charged hydrophilic form, the uncharged hydrophobic form is continuously reduced, the hydrophilicity of the hydrogel is continuously improved, the improvement of the hydrophilicity is beneficial to the release of a surfactant, the surface tension of the solution is reduced after the surfactant is released, the marangoni effect is formed, and therefore motor driving is achieved.
4) The hydrogel multistage motor obtained by the invention has excellent driving performance, the highest driving average speed can reach 16.2 +/-1.3 mm/s, the driving power of the multistage motor is derived from the reaction of phenylboronic acid in a driving layer and glucose in a driving environment to release sodium dodecyl sulfate in a matrix, the partial dissolution of a decomposition layer at the initial temperature of 28 ℃ greatly improves the driving performance of the multistage motor, and the two power sources cooperate to jointly propel the motion of the multistage motor, so that the multistage motor has very excellent driving performance.
5) The invention uses gelatin which can realize gel-sol transformation at low temperature as the main material of the decomposition layer, and simultaneously, the dissolving temperature of the mixed gel prepared by adding a proper amount of agar solution into the gelatin solution is increased along with the increase of the agar content, thus the dissolving temperature of each decomposition layer can be controlled, and the small motor can be released step by controlling the temperature.
6) The hydrogel multistage motor obtained by the invention is a self-carrying fuel type micro motor, has stronger environmental adaptability compared with most of chemical catalytic micro motors which can be driven by depending on external fuel, and widens the application range of the motor.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Example 1
(1) Drying 5mg of laponite (laponite) in an oven in advance, dispersing the laponite (laponite) in 1mL of ultrapure water after drying, stirring, and performing ultrasonic treatment in an ice bath for 30min to form a uniform laponite dispersion liquid.
(2) Adding 56.5mg of N-isopropylacrylamide, 19.1mg of 3-acrylamidophenylboronic acid, 9.3mg of N, N-methylenebisacrylamide and 17.3mg of sodium dodecyl sulfate into the laponite dispersion obtained in the step (1), stirring and dispersing uniformly, adding 3.4mg of 2,2' -azo (2-methylpropylamidine) dihydrochloride and 10 mu of L N of N, N ', N ' -tetramethylethylenediamine under the condition of keeping out of the light, ultrasonically mixing the mixed solution in an ice bath, and introducing 10min of nitrogen to remove oxygen dissolved in the mixed solution.
(3) Firstly, adding movable small silica gel mould blocks into large mould holes, quickly injecting the mixed solution into a mould, wherein the solution in each hole is 25 mu L, polymerizing for 3min under a high-intensity ultraviolet lamp (the power of the ultraviolet lamp is 1kW) after all the mould holes are injected, and taking out the movable small silica gel mould blocks after the polymerization is finished, so that a driving layer in the mould is obtained.
(4) Preparing gelatin/agar mixed solution with different proportions, wherein the solid content of the mixed solution is 10 wt%, the formula of the second-stage decomposition layer is GltAg0 (100 parts by mass of gelatin and 0 part by mass of agar), and the formula of the fourth-stage decomposition layer is GltAg2 (100 parts by mass of gelatin and 2 parts by mass of agar). During dissolution of the infrared controlled decomposition layer, 2 wt% (relative to the gelatin/agar mixing mass) of graphene nanoplatelets were added to the gelatin/agar mixed gel.
(5) After the driving layer is obtained in the step (3), 25 μ L of gelatin/agar mixed solution with different mixture ratio obtained in the step (4) is dropped into the spacing area in the mold, and finally, the mixture is placed in a refrigerator at 4 ℃ for 2.5h, the solution is gelled at low temperature, and after gelation, the mixture is separated from the mold, thus obtaining the hydrogel multistage motor with the driving layer and the decomposition layer alternated.
(6) Preparing a driving solution, in order to observe the driving process of the hydrogel multistage motor, adopting 0.02mol/L glucose solution as a driving energy source, adjusting the pH value of the solution to be 8 by using sodium bicarbonate, adjusting the ionic strength of the driving solution to be 0.15mol/L by using sodium chloride, and setting the initial temperature of the environment to be 28 ℃. The average driving speed of the multi-stage motor is 4 +/-0.5 mm/s.
(7) After a period of time with multi-stage motor drive, ambient temperature was raised to 31 ℃, the second stage of the GltAg0 gel layer dissolved, the first stage of the small motor was released and freely driven, the temperature was raised again to 32 ℃, the fourth stage of the GltAg2 gel layer dissolved, and the third stage of the small motor was released and freely driven.
(8) The dissolution of the GltAg can be controlled by near-infrared laser, and 2 wt% (relative to the mixed mass of gelatin and agar) of graphene nanosheets are added into the GltAg gel solution to obtain the GNS-GltAg gel. After the multi-stage motor is driven for a period of time, the GNS-GltAg0 gel layer is irradiated by near-infrared laser, after the gel layer is dissolved, the small motor at the first stage is released and freely driven, the GNS-GltAg2 gel layer is irradiated by near-infrared laser again, and after the gel layer is dissolved, the small motor at the third stage is released and freely driven.
Example 2
(1) 10mg of laponite (laponite) is dried in an oven in advance, and after drying, the laponite is dispersed in 1mL of ultrapure water and stirred, and ultrasonic treatment is carried out in an ice bath for 30min to form a uniform laponite dispersion liquid.
(2) Adding 60mg of N-isopropylacrylamide, 15mg of methacrylamide phenylboronic acid, 5.0mg of N, N-methylene bisacrylamide and 20.0mg of sodium dodecyl sulfate into the laponite dispersion liquid obtained in the step (1), stirring and dispersing uniformly, adding 2.5mg of 2,2' -azo (2-methylpropylamidine) dihydrochloride and 5 mu L N of N, N ', N ' -tetramethylethylenediamine under the condition of keeping out of the light, ultrasonically mixing the mixed liquid in an ice bath, and introducing 10min of nitrogen to remove oxygen dissolved in the mixed liquid.
(3) Firstly, adding movable small silica gel mould blocks into large mould holes, quickly injecting the mixed solution into a mould, wherein the solution in each hole is 15 mu L, polymerizing for 3min under a high-intensity ultraviolet lamp (the power of the ultraviolet lamp is 1kW) after all the mould holes are injected, and taking out the movable small silica gel mould blocks after the polymerization is finished, so that a driving layer in the mould is obtained.
(4) Preparing gelatin/agar mixed solution with different proportions, wherein the solid content of the mixed solution is 5 wt%, the formula of the second-stage decomposition layer is GltAg4 (100 parts by mass of gelatin and 4 parts by mass of agar), and the formula of the fourth-stage decomposition layer is GltAg8 (100 parts by mass of gelatin and 8 parts by mass of agar). During dissolution of the infrared controlled decomposition layer, 1 wt% (relative to the gelatin/agar mixing mass) of graphene nanoplatelets was added to the gelatin/agar mixed gel.
(5) After the driving layer is obtained in the step (3), 15 μ L of the gelatin/agar mixed solution of different ratios obtained in the step (4) is dropped into the spaced area in the mold, and finally, the mixture is placed in a refrigerator at 4 ℃ for 5 hours, the solution is gelled at low temperature, and after gelation, the mixture is separated from the mold, thus obtaining the hydrogel multistage motor with the driving layer and the decomposition layer alternated.
(6) Preparing a driving solution, in order to observe the driving process of the hydrogel multistage motor, adopting 0.03mol/L glucose solution as a driving energy source, adjusting the pH value of the solution to be 8 by using sodium bicarbonate, adjusting the ionic strength of the driving solution to be 0.2mol/L by using sodium chloride, and setting the initial temperature of the environment to be 28 ℃. The average driving speed of the multi-stage motor is 7.3 +/-0.8 mm/s.
(7) After a period of multi-stage motor drive, ambient temperature was raised to 32 ℃, the second stage of the GltAg4 gel layer dissolved, the first stage of the small motor was released and freely driven, the temperature was raised again to 38 ℃, the fourth stage of the GltAg8 gel layer dissolved, and the third stage of the small motor was released and freely driven.
(8) The dissolution of the GltAg can be controlled by near-infrared laser, and 2 wt% (relative to the mixed mass of gelatin and agar) of graphene nanosheets are added into the GltAg gel solution to obtain the GNS-GltAg gel. After the multi-stage motor is driven for a period of time, the GNS-GltAg4 gel layer is irradiated by near-infrared laser, after the gel layer is dissolved, the small motor at the first stage is released and freely driven, the GNS-GltAg8 gel layer is irradiated by near-infrared laser again, and after the gel layer is dissolved, the small motor at the third stage is released and freely driven.
Example 3
(1) Drying 5mg of laponite (laponite) in an oven in advance, dispersing the laponite (laponite) in 1mL of ultrapure water after drying, stirring, and performing ultrasonic treatment in an ice bath for 30min to form a uniform laponite dispersion liquid.
(2) Adding 56.5mg of acrylamide, 19.1mg of methacrylamide phenylboronic acid, 9.3mg of N, N-methylene bisacrylamide and 17.3mg of polyethylene glycol into the laponite dispersion liquid obtained in the step (1), stirring and dispersing uniformly, adding 4.5mg of 2,2' -azo (2-methylpropylamidine) dihydrochloride and 20 mu of L N, N, N ', N ' -tetramethylethylenediamine under the condition of keeping out of the light, ultrasonically mixing the mixed liquid in an ice bath uniformly, and introducing 10min of nitrogen to remove oxygen dissolved in the mixed liquid.
(3) Firstly, adding movable small silica gel mould blocks into large mould holes, quickly injecting the mixed solution into a mould, wherein the solution in each hole is 10 mu L, polymerizing for 3min under a high-intensity ultraviolet lamp (the power of the ultraviolet lamp is 1kW) after all the mould holes are injected, and taking out the movable small silica gel mould blocks after the polymerization is finished, so that a driving layer in the mould is obtained.
(4) Preparing gelatin/agar mixed solution with different proportions, wherein the solid content of the mixed solution is 10 wt%, the formula of the second-stage decomposition layer is GltAg0 (100 parts by mass of gelatin and 0 part by mass of agar), and the formula of the fourth-stage decomposition layer is GltAg2 (100 parts by mass of gelatin and 2 parts by mass of agar). During dissolution of the infrared controlled decomposition layer, 2 wt% (relative to the gelatin/agar mixing mass) of graphene nanoplatelets were added to the gelatin/agar mixed gel.
(5) After the driving layer is obtained in the step (3), 10 μ L of the gelatin/agar mixed solution of different ratios obtained in the step (4) is dropped into the spaced area in the mold, and finally, the mixture is placed in a refrigerator at 4 ℃ for 2 hours, the solution is gelled at low temperature, and after gelation, the mixture is separated from the mold, thus obtaining the hydrogel multistage motor with the driving layer and the decomposition layer alternated.
(6) Preparing a driving solution, in order to observe the driving process of the hydrogel multistage motor, adopting 0.03mol/L glucose solution as a driving energy source, adjusting the pH value of the solution to be 8 by using sodium bicarbonate, adjusting the ionic strength of the driving solution to be 0.3mol/L by using sodium chloride, and setting the initial temperature of the environment to be 28 ℃. The average driving speed of the multi-stage motor is 6.5 +/-0.7 mm/s.
(7) After a period of time with multi-stage motor drive, ambient temperature was raised to 31 ℃, the second stage of the GltAg0 gel layer dissolved, the first stage of the small motor was released and freely driven, the temperature was raised again to 32 ℃, the fourth stage of the GltAg2 gel layer dissolved, and the third stage of the small motor was released and freely driven.
(8) The dissolution of the GltAg can be controlled by near-infrared laser, and 2 wt% (relative to the mixed mass of gelatin and agar) of graphene nanosheets are added into the GltAg gel solution to obtain the GNS-GltAg gel. After the multi-stage motor is driven for a period of time, the GNS-GltAg0 gel layer is irradiated by near-infrared laser, after the gel layer is dissolved, the small motor at the first stage is released and freely driven, the GNS-GltAg2 gel layer is irradiated by near-infrared laser again, and after the gel layer is dissolved, the small motor at the third stage is released and freely driven.
Example 4
(1) 10mg of laponite (laponite) is dried in an oven in advance, and after drying, the laponite is dispersed in 1mL of ultrapure water and stirred, and ultrasonic treatment is carried out in an ice bath for 30min to form a uniform laponite dispersion liquid.
(2) Adding 100mg of acrylamide, 25mg of 3-acrylamidophenylboronic acid, 15mg of N, N-methylene bisacrylamide and 15mg of polyethylene glycol into the laponite dispersion liquid obtained in the step (1), stirring and dispersing uniformly, adding 3.4mg of alpha-aminoacetophenone and 10 mu L of tetramethylethylenediamine under the condition of keeping out of the sun, ultrasonically mixing the mixed liquid in an ice bath, and introducing 10min of nitrogen to remove oxygen dissolved in the mixed liquid.
(3) Firstly, adding movable small silica gel mould blocks into large mould holes, quickly injecting the mixed solution into a mould, wherein the solution in each hole is 15 mu L, polymerizing for 3min under a high-intensity ultraviolet lamp (the power of the ultraviolet lamp is 1kW) after all the mould holes are injected, and taking out the movable small silica gel mould blocks after the polymerization is finished, so that a driving layer in the mould is obtained.
(4) Preparing gelatin/agar mixed solution with different proportions, wherein the solid content of the mixed solution is 15 wt%, the formula of the second-stage decomposition layer is GltAg2 (100 parts by mass of gelatin and 2 parts by mass of agar), and the formula of the fourth-stage decomposition layer is GltAg10 (100 parts by mass of gelatin and 10 parts by mass of agar). During dissolution of the infrared controlled decomposition layer, 3 wt% (relative to the gelatin/agar mixing mass) of graphene nanoplatelets was added to the gelatin/agar mixed gel.
(5) After the driving layer is obtained in the step (3), 15 μ L of the gelatin/agar mixed solution of different ratios obtained in the step (4) is dropped into the spaced area in the mold, and finally, the mixture is placed in a refrigerator at 4 ℃ for 5 hours, the solution is gelled at low temperature, and after gelation, the mixture is separated from the mold, thus obtaining the hydrogel multistage motor with the driving layer and the decomposition layer alternated.
(6) Preparing a driving solution, in order to observe the driving process of the hydrogel multistage motor, adopting 0.05mol/L glucose solution as a driving energy source, adjusting the pH value of the solution to be 8 by using sodium bicarbonate, adjusting the ionic strength of the driving solution to be 0.3mol/L by using sodium chloride, and setting the initial temperature of the environment to be 28 ℃. The average driving speed of the multi-stage motor is 16.2 +/-1.3 mm/s.
(7) After a period of time with multi-stage motor drive, ambient temperature was raised to 32 ℃, the second stage of the GltAg2 gel layer dissolved, the first stage of the small motor was released and freely driven, the temperature was raised again to 41 ℃, the fourth stage of the GltAg10 gel layer dissolved, and the third stage of the small motor was released and freely driven.
(8) The dissolution of the GltAg can be controlled by near-infrared laser, and 2 wt% (relative to the mixed mass of gelatin and agar) of graphene nanosheets are added into the GltAg gel solution to obtain the GNS-GltAg gel. After the multi-stage motor is driven for a period of time, the GNS-GltAg2 gel layer is irradiated by near-infrared laser, after the gel layer is dissolved, the small motor at the first stage is released and freely driven, the GNS-GltAg10 gel layer is irradiated by near-infrared laser again, and after the gel layer is dissolved, the small motor at the third stage is released and freely driven.
Example 5
(1) Taking 15mg of laponite (laponite) and drying in an oven in advance, dispersing the laponite (laponite) in 1mL of ultrapure water after drying, stirring, and carrying out ultrasonic treatment in an ice bath for 30min to form a uniform laponite dispersion liquid.
(2) Adding 37.5mg of acrylamide, 15.0mg of 3-acrylamidophenylboronic acid, 10.0mg of N, N-methylene bisacrylamide and 20.0mg of polyethylene glycol into the laponite dispersion liquid obtained in the step (1), stirring and dispersing uniformly, adding 4.5mg of alpha-aminoacetophenone and 20 mu L of tetramethylethylenediamine under the condition of keeping out of the sun, ultrasonically mixing the mixed liquid in an ice bath, and introducing 10min of nitrogen to remove oxygen dissolved in the mixed liquid.
(3) Firstly, adding movable small silica gel mould blocks into large mould holes, quickly injecting the mixed solution into a mould, wherein the solution in each hole is 18 mu L, polymerizing for 3min under a high-intensity ultraviolet lamp (the power of the ultraviolet lamp is 1kW) after all the mould holes are injected, and taking out the movable small silica gel mould blocks after the polymerization is finished, so that a driving layer in the mould is obtained.
(4) Preparing gelatin/agar mixed solution with different proportions, wherein the solid content of the mixed solution is 15 wt%, the formula of the second-stage decomposition layer is GltAg4 (100 parts by mass of gelatin and 4 parts by mass of agar), and the formula of the fourth-stage decomposition layer is GltAg16 (100 parts by mass of gelatin and 16 parts by mass of agar). During dissolution of the infrared controlled decomposition layer, 4 wt% (relative to the gelatin/agar mixing mass) of graphene nanoplatelets was added to the gelatin/agar mixed gel.
(5) After the driving layer is obtained in the step (3), 18 μ L of the gelatin/agar mixed solution with different mixture ratios obtained in the step (4) is dropped into the spacing area in the mold, and finally, the mixture is placed in a refrigerator at 4 ℃ for 5 hours, the solution is gelled at low temperature, and after gelation, the mixture is separated from the mold, so that the hydrogel multistage motor with the driving layer and the decomposition layer alternated is obtained.
(6) Preparing a driving solution, in order to observe the driving process of the hydrogel multistage motor, adopting 0.05mol/L glucose solution as a driving energy source, adjusting the pH value of the solution to be 8 by using sodium bicarbonate, adjusting the ionic strength of the driving solution to be 0.3mol/L by using sodium chloride, and setting the initial temperature of the environment to be 28 ℃. The average driving speed of the multi-stage motor is 12.6 +/-1.0 mm/s.
(7) After a period of multi-stage motor drive, ambient temperature was raised to 32 ℃, the second stage of the GltAg16 gel layer dissolved, the first stage of the small motor was released and freely driven, the temperature was raised again to 65 ℃, the fourth stage of the GltAg20 gel layer dissolved, and the third stage of the small motor was released and freely driven.
(8) The dissolution of the GltAg can be controlled by near-infrared laser, and 2 wt% (relative to the mixed mass of gelatin and agar) of graphene nanosheets are added into the GltAg gel solution to obtain the GNS-GltAg gel. After the multi-stage motor is driven for a period of time, the GNS-GltAg4 gel layer is irradiated by near-infrared laser, after the gel layer is dissolved, the small motor at the first stage is released and freely driven, the GNS-GltAg16 gel layer is irradiated by near-infrared laser again, and after the gel layer is dissolved, the small motor at the third stage is released and freely driven.
Example 6
(1) And (3) drying 20mg of laponite (laponite) in an oven in advance, dispersing the laponite (laponite) in 1mL of ultrapure water after drying, stirring, and carrying out ultrasonic treatment in an ice bath for 30min to form a uniform laponite dispersion liquid.
(2) Adding 62.5mg of N-isopropylacrylamide, 25.0mg of methacrylamide phenylboronic acid, 10.0mg of N, N-methylene bisacrylamide and 18.0mg of polyethylene glycol into the laponite dispersion liquid obtained in the step (1), stirring and dispersing uniformly, adding 2.5mg of alpha-aminoacetophenone and 5 mu L of tetramethylethylenediamine under the condition of keeping out of the sun, ultrasonically mixing the mixed liquid in an ice bath, and introducing 10min of nitrogen to remove oxygen dissolved in the mixed liquid.
(3) Firstly, adding movable small silica gel mould blocks into large mould holes, quickly injecting the mixed solution into a mould, wherein the solution in each hole is 15 mu L, polymerizing for 3min under a high-intensity ultraviolet lamp (the power of the ultraviolet lamp is 1kW) after all the mould holes are injected, and taking out the movable small silica gel mould blocks after the polymerization is finished, so that a driving layer in the mould is obtained.
(4) Preparing gelatin/agar mixed solution with different proportions, wherein the solid content of the mixed solution is 6 wt%, the formula of the second-stage decomposition layer is GltAg0 (100 parts by mass of gelatin and 0 part by mass of agar), and the formula of the fourth-stage decomposition layer is GltAg12 (100 parts by mass of gelatin and 12 parts by mass of agar). During dissolution of the infrared controlled decomposition layer, 1 wt% (relative to the gelatin/agar mixing mass) of graphene nanoplatelets was added to the gelatin/agar mixed gel.
(5) After the driving layer is obtained in the step (3), 15 μ L of the gelatin/agar mixed solution of different ratios obtained in the step (4) is dropped into the spaced area in the mold, and finally, the mixture is placed in a refrigerator at 4 ℃ for 4 hours, the solution is gelled at low temperature, and after gelation, the mixture is separated from the mold, thus obtaining the hydrogel multistage motor with the driving layer and the decomposition layer alternated.
(6) Preparing a driving solution, in order to observe the driving process of the hydrogel multistage motor, adopting 0.04mol/L glucose solution as a driving energy source, adjusting the pH value of the solution to be 8 by using sodium bicarbonate, adjusting the ionic strength of the driving solution to be 0.18mol/L by using sodium chloride, and setting the initial temperature of the environment to be 28 ℃. The average driving speed of the multi-stage motor is 10 +/-0.9 mm/s.
(7) After a period of time with multi-stage motor drive, ambient temperature was raised to 31 ℃, the second stage of the GltAg0 gel layer dissolved, the first stage of the small motor was released and freely driven, the temperature was raised again to 46 ℃, the fourth stage of the GltAg12 gel layer dissolved, and the third stage of the small motor was released and freely driven.
(8) The dissolution of the GltAg can be controlled by near-infrared laser, and 2 wt% (relative to the mixed mass of gelatin and agar) of graphene nanosheets are added into the GltAg gel solution to obtain the GNS-GltAg gel. After the multi-stage motor is driven for a period of time, the GNS-GltAg0 gel layer is irradiated by near-infrared laser, after the gel layer is dissolved, the small motor at the first stage is released and freely driven, the GNS-GltAg12 gel layer is irradiated by near-infrared laser again, and after the gel layer is dissolved, the small motor at the third stage is released and freely driven.
Claims (10)
1. A glucose-responsive driven hydrogel multistage motor, comprising: the drive layer of the hydrogel multistage motor is phenyl boric acid hydrogel with glucose response drive, the decomposition layer is gelatin/agar mixed gel capable of realizing gel-sol conversion at low temperature, and the dissolution temperature of the gelatin/agar mixed gel is continuously improved along with the increase of agar content, so that in the hydrogel multistage motor, the decomposition layer adopts the gelatin/agar mixed gel with different proportions, different dissolution temperatures of each decomposition layer in the hydrogel multistage motor are realized, and good control is provided for the small motors for gradual dissolution and release of the decomposition layers.
2. A method of making a glucose-responsive driven hydrogel multistage motor of claim 1 comprising the steps of:
(1) dispersing the dried laponite in water, stirring, and ultrasonically treating in an ice bath to form a uniform laponite dispersion liquid;
(2) adding a water gel monomer, a chemical cross-linking agent and a surfactant into the laponite dispersion liquid obtained in the step (1), stirring and dispersing uniformly, adding a photoinitiator and a catalyst under the condition of keeping out of the sun, ultrasonically mixing the mixed liquid uniformly in an ice bath, and introducing nitrogen to remove oxygen dissolved in the mixed liquid;
(3) adding movable small silica gel mold blocks into a large mold hole, injecting the mixed solution obtained in the step (2) into the large mold hole, polymerizing under a high-intensity ultraviolet lamp after all the mold holes are injected, and taking out the movable small silica gel mold blocks after the polymerization is finished to obtain a driving layer in the mold;
(4) preparing gelatin/agar mixed solutions with different ratios, wherein each decomposition layer adopts gelatin/agar mixed gel with different ratios, and the content of agar in the decomposition layer is gradually increased; in the temperature-controlled dissolving process, in order to better observe the dissolving phenomenon of a decomposition layer in a driving environment, a gelatin/agar mixed solution is dyed by using a water-soluble dye; meanwhile, in the infrared irradiation dissolving process, in order to enable the decomposition layer to obtain more energy from the infrared laser, adding graphene nanosheets into the gelatin/sol mixed solution;
(5) and (3) after the driving layer is obtained in the step (3), dripping the gelatin/agar mixed solution with different ratios obtained in the step (4) into a spacing area in a mould, standing to gelatinize the mixed solution, and separating from the mould to obtain the hydrogel multistage motor with the driving layer and the decomposition layer alternated.
3. The method of claim 2, wherein: the dosage of the laponite in the step (1) is 0.5-2% of the mass of the water in the step (1).
4. The method of claim 2, wherein: the hydrogel monomer in the step (2) is two types of monomers, namely an olefin water-soluble monomer with a double bond and an amide group and an olefin hydrophobic monomer with a phenylboronic acid group.
5. The method of claim 4, wherein: the olefin water-soluble monomer is one or more of acrylamide and N-isopropyl acrylamide; the olefin hydrophobic monomer is one or more of 3-acrylamido phenylboronic acid and methacrylamide phenylboronic acid; the olefin hydrophobic monomer accounts for 25 to 40 percent of the mass of the olefin water-soluble monomer; the dosage of the olefin hydrophobic monomer is 1.5-2.5% of the mass of the water in the step (1).
6. The method of claim 2, wherein:
the chemical cross-linking agent in the step (2) is N, N-methylene bisacrylamide, and the using amount of the chemical cross-linking agent is 0.50-1.5 percent of the mass of the water in the step (1);
the surfactant is sodium dodecyl sulfate or polyethylene glycol, and the using amount of the surfactant is 1.5-2.0% of the mass of the water in the step (1);
the photoinitiator is 2,2' -azo (2-methylpropylamidine) dihydrochloride or alpha-aminoacetophenone, and the using amount of the photoinitiator is 0.25 to 0.45 percent of the mass of the water in the step (1);
the catalyst is N, N, N ', N' -tetramethyl ethylenediamine, and the using amount of the catalyst is 0.5-2.0% of the volume of the water in the step (1).
7. The method of claim 2, wherein: and (4) the volume of the mixed solution injected into the hole of the single mould in the step (3) is 10-25 mu L, and then the driving layer is obtained by adopting photo-initiation polymerization.
8. The method of claim 2, wherein: the total mass of the gelatin and the agar in the gelatin/agar mixed solution in the step (4) is 5-15% of the mass of the water in the step (1), wherein the mass of the agar is 2-16% of the mass of the gelatin; the graphene nanosheet accounts for 1-4% of the mixed mass of gelatin and agar.
9. The method of claim 2, wherein: the volume of the gelatin/agar mixed solution injected into each of the spaced mold holes in step (5) is the same as the volume of the driving layer in step (3), and is 10. mu.L to 25. mu.L.
10. The method of claim 2, wherein: the step (5) of gelatinizing the solution is to gelatinize the solution in a refrigerator at 4 ℃ for 2 to 5 hours.
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